Processing Stabilisation of PE with a Natural Antioxidant ...real.mtak.hu/5496/1/Tatraaljai EPJ 2013...
Transcript of Processing Stabilisation of PE with a Natural Antioxidant ...real.mtak.hu/5496/1/Tatraaljai EPJ 2013...
European Polymer Journal 49 (2013) 1196-1203 doi: http://dx.doi.org/10.1016/j.eurpolymj.2013.02.018
Processing Stabilisation of PE with a Natural Antioxidant, Curcumin
Dóra Tátraaljai1,2, Balázs Kirschweng1,2, János Kovács1,2, Enikő Földes1,2*,
Béla Pukánszky1,2
1Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences,
Hungarian Academy of Sciences, H-1525 Budapest, P.O. Box 17, Hungary
2Laboratory of Plastics and Rubber Technology, Department of Physical Chemistry and
Materials Science, Budapest University of Technology and Economics, H-1521 Budapest,
P.O. Box 91, Hungary
Abstract
The potential use of natural antioxidants for polyolefin stabilisation came into the
centre of attention because of some doubts about the effects of the reaction products of
synthetic phenolic antioxidants on human health. The effect of curcumin on the melt stability
of polyethylene was investigated in this paper with and without a phosphonite stabiliser by
using multiple extrusions. Irganox 1010 was applied as reference phenolic antioxidant.
Curcumin was characterised by FT-IR and UV-VIS spectroscopy, as well as by thermal
analysis. Its stabilisation efficiency was determined by measuring the chemical structure, the
rheological properties, the residual thermo-oxidative stability, and the colour of the polymer.
The results reveal that the melt stabilising efficiency of curcumin is superior to that of the
synthetic antioxidant investigated and is further enhanced by the addition of the phosphonite
secondary antioxidant. The changes in the characteristics of the polymer indicate that besides
the phenolic OH groups also the linear linkage between the two methoxyphenyl rings of
curcumin participates in the stabilisation reactions.
*to whom correspondence should be addressed, E-mail: [email protected]
Key words: natural antioxidant, curcumin, polyethylene, stabilisation
1. Introduction
Polyethylene (PE) is a commodity polymer applied in many areas. The material is
exposed to heat, shear, and a small amount of oxygen during processing. Without adequate
stabilisation this leads to degradation reactions: chain scission and/or chain extension, which
result in the deterioration of mechanical properties and ultimately the formation of a network.
Synthetic antioxidants are used to hinder these reactions in practice, but several questions
were raised earlier regarding the effect of the reaction products of phenolic antioxidants on
human health, which have not been answered yet [1]. Accordingly, the interest is focused
more and more on the potential use of natural antioxidants for the stabilisation of polymers
[e.g., 2-8]. The aim of our research was to find natural antioxidants, which can efficiently
hinder the degradation of polyethylene during processing without any danger of possible
health damage when dissolving from the polymer during application. The use of natural
antioxidants eventually may even have some positive physiological effects. In this study we
investigated the effect of curcumin on the processing stability of PE and compared to that of
the most commonly used phenolic antioxidant, Irganox 1010 (see chemical structure in Table
1).
Curcumin, 1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, is the
principal curcuminoid of Curcuma longa rhizomes (turmeric). The curcuminoids are natural
phenols that cause the yellow color of turmeric [9]. Curcumin is an oil-soluble pigment,
practically insoluble in water at acidic and neutral pH, and soluble in alkali [10]. Curcumin
can exist in several tautomeric forms, including a 1,3-diketo form and two equivalent enol
forms (Table 1). In solid state and in many solutions the planar enol form is more stable than
2
the nonplanar diketo form [11], while the keto form predominates in acidic and neutral
aqueous solutions and in the cell membrane [12]. Curcumin has superb antioxidant activity
which was found to be stronger for the enol isomer than the for keto form [13]. This
antioxidant has radical and hydrogen peroxyde scavenging, as well as metal chelating
activities [e.g., 14-17]. Besides scavenging oxygen centred radicals curcumin also scavenges
nitrogen centred free radicals [18,19]. The antioxidant and antifungal activities of curcumin is
enhanced when used in combination with ascorbic acid [20].
Curcumin is not particularly stable to light, especially in solutions [10]. A cyclic as well
as other decomposition products, such as vanillic acid, vanillin, and ferulic acid were detected
in its solutions after photo-irradiation [10,21,22]. The photosenzitization of curcumin requires
oxygen [23]. In solid state the intramolecular hydrogen bonding provides a channel for fast
deactivation of excited states [24]. In solution the photochemical properties are strongly
influenced by the type of solvent. In protic solvents, like ethanol, both parts of the curcumin
molecule are involved in the excited singlet state. Curcumin photogenerates singlet oxygen,
superoxide, as well as some carbon-centred radicals in this solvent [24].
Powdered turmeric rhizomes is used as food colorant, spice and food preservative. The
medical activity of curcumin has been known since ancient times. As a consequence, the
different effects and reactions of curcumin have been the subject of investigation in the fields
of biology, medicine, pharmacology, as well as in the food industry for many years yielding a
large number of publications. However, the actual reaction site and the mechanism of free
radical scavenging have not been clarified yet. H-atom donation was found as a preferred
reaction of curcumin at pH ≤ 7 and in nonprotic solvents [12]. Barclay et al. [25] observed
that the antioxidant activities of o-methoxyphenols decreased in hydrogen bond accepting
media. According to some authors the OH groups on the two phenyl rings participate in the
reactions [e.g.,13,14,25], others claim that the β-diketone moiety is responsible for the
3
antioxidant action [12], while other publications [26,27] indicate that the strong antioxidant
activity of curcumin originates mainly from the phenolic OH groups, but a small fraction is
due to the >CH2 site in the β-diketone moiety. Not only the site but also the reaction
mechanism of antioxidant activity is controversial. Some authors [e.g., 12,26,28] proposed H-
atom transfer (HAT), some others [29] suggested single electron transfer (SET) mechanism,
while Litwinienko and Ingold [30,31] elaborated the Sequential Proton Loss Electron Transfer
(SPLET) theory.
The antioxidant activity of curcumin is usually studied in solution at ambient
temperature. The question is whether this natural antioxidant can keep its superb stabilising
efficiency under the conditions of polyolefin processing (190-260 °C, shear). We could not
find any publication dealing with this aspect. In this work the stabilisation effect of curcumin
was studied in polyethylene processed by multiple extrusions. The natural antioxidant was
investigated as a singly stabiliser and in combination with a phosphorous secondary
antioxidant, which plays an important role in the processing stabilisation of polyethylene
[32,33]. The stabilising efficiency of curcumin was compared to that of a commonly used
synthetic phenolic antioxidant.
2. Experimental 2.1. Materials
The experiments were carried out with the Tipelin FS 471 grade ethylene/1-hexene
copolymer (melt flow rate of the powder: 0.32 g/10 min, nominal density: 0.947 g/cm3)
polymerized by a Phillips catalyst. The additive-free polymer powder was provided by Tisza
Chemical Ltd. (TVK), Hungary. The polymer was stabilised with 1000 ppm curcumin (Sigma-
Aldrich), and with a mixture of 1000 ppm curcumin and 2000 ppm Sandostab P-EPQ (P-EPQ;
Clariant). Samples processed with the same amounts of Irganox 1010 (I1010; BASF
4
Switzerland) and its combination with P-EPQ were used as references. The chemical structure
of the investigated antioxidants, including the components of P-EPQ which is a mixture of
three compounds, is shown in Table 1.
2.2. Sample preparation
The polymer and the additives were homogenized in a high speed mixer (Henschel
FM/A10) at a rate of 500 rpm for 10 min then pelletized by six consecutive extrusions using a
Rheomex S ¾” type single screw extruder attached to a Haake Rheocord EU 10V driving unit
at 50 rpm and barrel temperatures of 180, 220, 260 and 260 °C. Samples were taken after each
extrusion step. For further studies films of about 100 µm and plates of 1 mm thickness were
compression moulded at 190 °C using a Fontijne SRA 100 machine.
2.3. Methods
The chemical structure of curcumin and the functional groups (unsaturated and
carbonyl) of polyethylene were investigated by FT-IR spectroscopy using a Tensor 27
(Bruker) type FT-IR spectrophotometer. Five parallel measurements were carried out on each
sample. The concentration of vinyl and carbonil groups were determined from the absorbance
spectra recorded on compression moulded polymer films by the internal standard method
according to Eq. 1
ref
inv
A
AKC
(1)
where C is the concentration of a given functional group, K is its absorption coefficient, is
the density of the polymer (g/cm3), while Ainv and Aref are the intensities of the investigated
and the reference absorption bands, respectively. We used the absorption band of the -CH
vibration appearing at 2018 cm-1 as reference. A series of Phillips type ethylene/1-hexene
5
copolymers with various butyl branching and unsaturations were investigated earlier to
determine the absorption coefficient of vinyl group vibration (band at 908 cm-1) (K = 0.5000).
The concentration of the carbonyl groups was calculated from the integrated absorption
intensity (TCO) of the vibration appearing in the range of 1780–1690 cm-1 (K = 0.03826).
The photo stability of curcumin was studied by aging the material in powder form and
in different solutions (ethanol, methanol, acetone, acetonitrile, toluol, chloroform) in natural
light (behind a window), and in dark with periodical sampling for 5 months. 5 mg of the
sample was dissolved in 100 ml solvent and analyzed by a HP 8452A type (Hewlett-Packard)
UV-VIS spectrophotometer in the wavelength range of 190-820 nm. The melting
characteristics and thermal stability of curcumin as well as its 1:1 mixture with P-EPQ were
studied using a Mettler TA 4000 Thermal Analyzer. Differential scanning calorimetric (DSC)
measurements were carried out in a DSC-30 cell under nitrogen (50 ml/min) at a heating rate
of 10 oC/min, from -50 to 300 °C.
The rheological properties of the polymer were measured by two methods. MFR
measurements were run according to the ASTM D 1238-79 standard at 190 C with 2.16 load
in a Göttfert MPS-D MFR tester. Creep curves were recorded at 190 °C with 500 Pa mean
stress and 300 s creep/600 s recovery phase times using a Rheoplus/32 V3.40 type (Anton
Paar) Universal Dynamic Spectrometer. Creep viscosity (0) was derived from the
compliance measured in the creep phase. The thermo-oxidative stability of the polymer was
characterised by the oxidation induction time (OIT) measured at 200 °C by a Perkin Elmer DSC-
2 apparatus under oxygen. The colour of the samples was determined using a Hunterlab
Colourquest 45/0 apparatus. Yellowness (YI) index was calculated as the characteristic
parameter.
6
3. Results and discussions
3.1. Stability and interactions of curcumin
We made an attempt to prove the H-bonding capability of curcumin by an FT-IR study
carried out in methanol solution. Unfortunately we failed completely, because of the intense
absorption of methanol made the determination any shift in absorption bands impossible.
However, thermal analysis offered an indirect way to prove the existence of such molecular
interactions. The melting traces of curcumin, P-EPQ, and the 1:1 mixture of curcumin and P-
EPQ (Fig. 1) were recorded under nitrogen after melting the materials in Ar atmosphere at
220 °C for 1 min followed by cooling to ambient temperature. The blend of the two additives,
i.e. cucumin and P-EPQ was studied in a similar way. Equal amounts of the two powders
were thoroughly mixed and melted under the conditions indicated above (220 °C, Ar). We
assumed that after melting the mixture became homogeneous. Curcumin fuses at 179 °C then
starts to decompose above 190 °C with an exothermal peak at 277 °C. P-EPQ does not
crystallise, it goes through glass transition with an overheating peak at 69.5 °C. The heat flow
does not change up to 265 °C at which the substance starts to decompose giving an
exothermal peak with a maximum at around 293 °C. Interaction between curcumin and P-
EPQ in the mixture is indicated by the shift of the glass transition of P-EPQ to 66 °C and the
disappearance of the fusion peak of curcumin. The mixture of the two additives is thermally
less stable than the components themselves. These phenomena could be the result of H-
bonding or other intermolecular interactions. The reactions resulting in exothermal heat flow
start at around 140 °C and show a maximum at 207 °C.
Curcumin was aged at ambient temperature in powder form and in methanol solution in
dark and light for 147 days. The UV-VIS absorption spectra shown in Fig. 2 reveal that the
chemical structure of the antioxidant does not change significantly when it is stored in powder
form either in dark or in light for five months, which, according to literature references [24],
7
can be explained with intramolecular hydrogen bonding that provides a channel for fast
deactivation of excited states [24]. The oxygen penetration into the crystals is also slower in
the solid resulting in slower decomposition, because of the absence of oxygen. Similarly, only
a small change can be observed when curcumin is dissolved in methanol and stored in dark
(Fig. 2). On the other hand, photochemical decomposition is revealed by the UV-VIS spectra
when the antioxidant is stored in methanol solution in light (Fig. 3). The fragmentation of the
molecule [22] is proved by the fast decrease in the intensity of the absorption bands appearing
at 424 and 262 nm and the increase in those detected at 232 and 200 nm wavelengths.
In order to confirm the specific effect of H-bonding on the stability of curcumin, we
carried out an ageing study in various solvents. Fig. 4 shows that in the two solvents which
can form strong H-bonds with curcumin, i.e. in ethanol and methanol, degradation is much
slower than in any of the other solvents thus proving the important role of specific interactions
on curcumin stability. These results are in accordance with the work of Nardo et al. [34].
Electronically excited β-diketones can deactivate in the fastest way by excited-state
intramolecular proton transfer (ESIPT). Intermolecular H-bond formation heavily perturbs
intramolecular H-bonding. The higher the ESIPT rate is the tighter the intramolecular H-bond
is between the enol and the keto moiety.
3.2. Processing stabilisation
The vinyl group concentration of the nascent polymer powder decreases the most
significantly (from 0.983 to 0.805 vinyl/1000 C) in the first extrusion then the change
becomes smaller in further processes (Fig. 5). The total decrease is only 0.025 vinil/1000 C in
the five consecutive extrusions. The composition of the stabiliser system does not influence
significantly the vinyl group content of the polymer. This result means that curcumin does not
change the reactions of the vinyl groups during processing compared to the effect of I1010.
8
Curcumin hinders the oxidation of polyethylene during processing more efficiently than
I1010 (Fig. 6). Carbonyl groups do not form in its presence or when its combination with P-
EPQ is used, while the oxidation of the polymer stabilised with the synthetic phenolic
antioxidant is proved by the carbonyl concentration which is larger than the one caused by
1000 ppm I1010 (0.1 mmol CO/mol PE). The degree of oxidation is smaller when I1010 is
combined with the phosphonite antioxidant.
Similarly to vinyl group content, the melt flow rate of the polymer decreases the most
significantly in the first extrusion, in an extent depending on the amount of P-EPQ (from 0.32
g/10 min to 0.17 and 0.20 g/10 min at 0 and 2000 ppm P-EPQ, respectively), as shown in Fig.
7. The addition of the phosphonite enhances the melt stabilising efficiency of both
antioxidants, while the type of the phenol derivative does not influence the change
significantly. In further extrusion processes the change in MFR is much smaller and the type
of the phenol plays an essential role in its direction. In the presence of I1010 the decrease in
MFR continues, while some increase can be observed with curcumin. This latter result
indicates that besides chain extension processes (characteristic for the degradation of Phillips
type polyethylenes) chain breaking also takes place. Similar conclusions can be drawn from
the changes in creep viscosity plotted as a function of the number of extrusions in Fig. 8. 0
increases considerably when I1010 is applied as a phenolic antioxidant, while it increases
only slightly when the polymer is stabilised with curcumin or does not change when the
curcumin/P-EPQ combination is used.
The residual thermo-oxidative stability of the polymer characterized by the oxidation
induction time is influenced by both types of antioxidants (Fig. 9). Without phosphonite the
phenolic antioxidants provides only moderate thermo-oxidative stability to the polymer,
although stability is independent of the number of extrusions. OIT increases considerably
when phenol/phosphonite antioxidant combinations are applied. With increasing number of
9
extrusions the phosphonite is consumed and the thermo-oxidative stability of the polymer
decreases. Fig. 9 also reveals that the same amount of curcumin is somewhat more efficient
oxidative stabiliser than I1010, either alone or in combination with P-EPQ.
The yellowness index of the samples is plotted as a function of the number of extrusions
in Fig. 10. I1010 discolours the polymer in a given degree, as known, and yellowness index
increases with increasing number of extrusions. The addition of P-EPQ to I1010 improves the
colour stability of the polymer, but some gradual yellowing cannot be avoided during multiple
extrusions even in this case. Due to its original yellow colour, curcumin discolours the
polymer quite strongly. The addition of P-EPQ to curcumin does not change yellowness
index. In contrast to the effect of I1010, the YI of the samples stabilised with curcumin
slightly decreases with increasing number of extrusions indicating that the heptadienone
linkage between the two methoxyphenol rings of curcumin also participates in the chemical
reactions taking place during the processing of polyethylene.
3.3. Discussion
The effect of curcumin on the processing stability of polyethylene can primarily be
explained with its ability to scavenge free radicals. The oxidation of the macroradicals formed
as an effect of heat and shear cannot be hindered in the first extrusion of the polymer powder,
as it contains absorbed oxygen at a relatively large concentration [35]. As a consequence, the
reactions of the polymer are controlled primarily by the number of unsaturated groups and the
efficiency of the hydroperoxide decomposing phosphorous secondary antioxidant [32,33]. In
further processes, in which thermal reactions dominate, the reaction mechanism of the
phenolic antioxidant plays an important role. In the case of I1010 the abstraction of the H-
atom from the phenolic OH group proceeds slower or with similar rate as the addition of
macroradicals to vinyl groups resulting in the formation of long chain branches, an increase of
10
viscosity and decrease of MFR. Due to its complex structure curcumin may participate in
several types of reactions. It can donate H atoms not only from the phenolic OH groups but
also from the linear linkage between the two methoxyphenyl rings. β-diketone radicals are
assumed to form by H atom donation from the CH2 group of the heptadienone linkage [26]
and they may react with the vinyl groups of the polymer and/or with macroradicals. Further
radicals can form also by the thermal decomposition of curcumin, which is not the subject of
investigation in the literature, since degradation is studied practically always in solution,
generally at ambient temperature [22,36]. Further possibility is the addition of macroradicals
to the unsaturated groups of the linear linkage of curcumin. The reactions of the radicals
derived from curcumin through reactions with the vinyl group of the polymer, and the
addition of macroradicals to the double bonds of curcumin can hinder the formation of long
chain branches. In this case the molecular mass of the polymer decreases, which results in an
increase of MFR and decrease of discolouration. The exact processing and thermo-oxidative
stabilisation mechanism of curcumin in polyethylene needs further studies. Model
experiments are in progress, and our first results show that curcumin is able to scavenge alkyl
radicals indeed, while Irganox 1010 can not. This additional capability may result in the larger
efficiency of curcumin compared to that of I1010.
4. Conclusions
Curcumin, a natural antioxidant, is stable as a crystalline solid at ambient temperature in
air. It keeps its stability in different kind of solutions when stored in dark, but decomposes in
light. Its rate of decomposition depends on the solvent used. Curcumin is thermally stable up
to 190 °C, but the interaction with a phosphonite stabiliser results in some decrease in the
starting temperature of thermal decomposition. Curcumin is a more efficient melt and thermo-
oxidative stabiliser of polyethylene than the synthetic phenolic antioxidant used as reference
11
(I1010), and the addition of a phosphonite secondary stabiliser improves its efficiency further.
Although the number of vinyl groups participating in chemical reactions during processing is
similar in the case of the two phenolic derivatives, changes in the rheological properties and
colour of the polymer reveal that the mechanism of their stabilization reactions differs. The
synthetic phenolic antioxidant used cannot hinder reactions leading to the formation of long
chain branches. In the presence of curcumin the melt flow rate of the polymer increases and
its colour decreases with increasing number of extrusions. These changes indicate that besides
the phenolic OH groups also the linear linkage between the two methoxyphenyl rings of
curcumin participates in the stabilisation reactions.
Acknowledgement
The National Research Fund of Hungary (OTKA K 77860 and K 101124) is greatly
acknowledged for the financial support of the research.
References
1. Brocca D, Arvin E, Mosbaek H. Identification of organic compounds migrating from
polyethylene pipelines into drinking water. Water Res 2002;36:3675-3680.
2. Al-Malaika S, Ashley H, Issenhuth S. The antioxidant role of α-tocopherol in polymers. I.
The nature of transformation products of α-tocopherol formed during melt processing of
LDPE. J Polym Sci Part A: Polym Chem 1994;32:3099-3113.
3. Al-Malaika S, et al. The antioxidant role of vitamin E in polymers V. Separation of
stereoisomers and characterisation of other oxidation products of dl-α-tocopherol formed
in polyolefins during melt processing. Polym Degrad Stab 2001;73:491-503.
4. Alexy P, Košíková B, Podstránska G. The effect of blending lignin with polyethylene and
polypropylene on physical properties. Polymer 2000;41:4901-4908.
12
5. de Abreu DAP, Losada PP, Maroto J, Cruz JM. Natural antioxidant active packaging film
and its effect on lipid damage in frozen blue shark (Prionace glauca). Innov Food Sci
Emerg Technol 2011;12:50-55.
6. de Abreu DAP, Maroto J, Rodríguez KV, Cruz JM. Antioxidants from barley husks
impregnated in films of low-density polyethylene and their effect over lipid deterioration
of frozen cod (Gadus morhua). J Sci Food Agr 2012;92:427-432.
7. Cerruti P, Malinconico M, Rychly J, Matisova-Rychla L, Carfagna C. Effect of natural
antioxidants on the stability of polypropylene films. Polym Degrad Stab 2009;94:2095-
2100.
8. Ambrogi V, Cerruti P, Carfagna C, Malinconico M, Marturano V, Perrotti M, Persico P.
Natural antioxidants for polypropylene stabilization. Polym Degrad Stab 2011;96:2152-
2158.
9. Phytopharmaceuticals in Cancer Chemoprevention, CRC Press LLC 2005; Ed.: Bagchi
D, Preuss HG, Chap. 23: Aggarwal BB, Kumar A, Aggarwal MS, Shishodia S. Curcumin
Derived from Turmeric (Curcuma longa): a Spice for All Seasons p.: 350-351.
10. Curcumin. CTA. (First draft Stankovic I) 61st JECFA. FAO 2004.
http://www.fao.org/fileadmin/templates/agns/pdf/jecfa/cta/61/Curcumin.pdf
11. Kolev TM, Velcheva EA, Stamboliyska BA, Spiteller M. DFT and experimental studies
of the structure and vibrational spectra of curcumin. Int J Quantum Chem
2005;102:1069–1079.
12. Jovanovic SV, Steenken S, Boone CW, Simic MG. H-atom transfer is a preferred
antioxidant mechanism of curcumin. J Am Chem Soc 1999;121:9677-9681.
13. Barzegar A. The role of electron-transfer and H-atom donation on the superb antioxidant
activity and free radical reaction of curcumin. Food Chem 2012;135:1369-1376.
14. Ak T, Gülçin I. Antioxidant and radical scavenging properties of curcumin. Chemico-
13
Biol Interact 2008;174:27-37.
15. Borsari M, Ferrari E, Grandi R, Saladini M. Curcuminoids as potential new iron-
chelating agents: spectroscopic, polarographic and potentiometric study on their Fe(III)
complexing ability. Inorg Chim Acta 2002;328:61-68.
16. Agnihotri N, Mishra PC. Scavenging mechanism of curcumin toward the hydroxyl
radical: A theoretical study of reactions producing ferulic acid and vanilin. J Phys Chem
2011;115:14221-1432.
17. Anto RJ, Kuttan G, Dinesh Babu KV, Rajasekharan KN, Kuttan R. Anti-tumour and free
radical scavenging activity of synthetic curcuminoids. Int J Pharm 1996;131:1-7.
18. Unnikrishnan MK, Rao MNA. Curcumin inhibits nitrogen dioxide induced oxidation of
hemoglobin. Mol Cell Biochem 1995;146:35-37.
19. Sreejayan N, Rao MNA. Free radical scavenging activity of curcuminoids. Arzneim-
Forsch/Drug Res 1996;46:169-171.
20. Khalil OAK, de Faria Oliveira OMM, Vellosa JCR, de Quadros AU, Dalposso LM,
Karam TK, Mainardes RM, Khalil NM. Curcumin antifungal and antioxidant activities
are increased in the presence of ascorbic acid. Food Chem 2012;133:1001-1005.
21. Tonnesen HH, Greenhill JV. Studies on curcumin and curcuminoids. XXII: Curcumin as
a reducing agent and as a radical scavenger. Int J Pharmaceut 1992;87:79-87.
22. Sundaryono A, Nourmamode A, Gardrat C, Grelier S, Bravic G, Chasseau D, Castellan
A. Studies on the photochemistry of 1,7-diphenyl-1,6-heptadiene-3,5-dione, a non-
phenolic curcuminoid model. Photochem Photobiol Sci 2003;2:914-920.
23. Dahl TA, McGowan WM, Shand MA, Srinivasan VS. Photokilling of bacteria by natural
dye curcumin. Arch Mikrobiol 1989;151:183-185.
24. Chignell CF, Bilski P, Reszka KJ, Motten AG, Sik RH, Dahl TA. Spectral and
photochemical properties of curcumin. Photochem Photobiol 1994;59:295-302.
14
25. Barclay LRC, Vinqvist MR, Mukai K, Goto H, Hashimoto Y, Tokunaga A, Uno H. On
the antioxidant mechanism of curcumin: classical methods are needed to determine
antioxidant mechanism and activity. Org Lett 2000;2(18):2841-2843.
26. Priyadarsini KI, Maity DK, Naik GH, Kumar MS, Unnikrishnan MK, Satav JG, Mohan
H. Role of phenolic O-H and methylene hydrogen on the free radical reactions and
antioxidant activity of curcumin. Free Radical Bio Med 2003;35:475-484.
27. Kim MK, Jeong W, Kang J, Chong Y. Significant enhancement in radical-scavenging
activity of curcuminoids conferred by acetoxy substituent at the central methylene
carbon. Bioorg Med Chem 2011;19:3793-3800.
28. Gorman AA, Hamblett I, Srinavasan VS, Wood PD. Curcumin-derived transients: a
pulsed laser and pulse radiolysis study. Photochem Photobiol 1994;59:389-398.
29. Galano A, Álvarez-Diduk R, Ramírez-Silva MT, Alarcón-Ángeles G, Rojas-Hernández.
Role of the reacting free radicals on the antioxidant mechanism of curcumin. Chem Phys
2009;363:13-23.
30. Litwinienko G, Ingold KU. Abnormal solvent effects on hydrogen atom abstraction. 2.
Resolution of the curcumin antioxidant controversy. The role of sequential proton loss
electron transfer. J Org Chem 2004;69:5888-5896.
31. Litwinienko G, Ingold KU. Solvent effects on the rates and mechanisms of reaction of
phenols with free radicals. Acc Chem Res 2007;40:222-230.
32. Kriston I, Orbán-Mester Á, Nagy G, Staniek P, Földes E, Pukánszky B. Melt stabilisation
of Phillips type polyethylene, Part I: The role of phenolic and phosphorous antioxidants,
Polym Degrad Stab 2009;94:719-29.
33. Kriston I, Orbán-Mester Á, Nagy G, Staniek P, Földes E, Pukánszky B. Melt stabilisation
of Phillips type polyethylene, Part II: Correlation between additive consumption and
polymer properties, Polym Degrad Stab 2009;94:1448-56.
15
34. Nardo L, Paderno R, Andreoni A, Másson M, Haukvik T, Tonnesen HH. Role of H-bond
formation in the photoreactivity of curcumin. Spectroscopy 2008;22:187–198.
35. Epacher E, Tolvéth J, Kröhnke C, Pukánszky B. Processing stability of high density
polyethylene: effect of adsorbed and dissolved oxygen. Polymer 2000;41:8401-8408.
36. Wang Y-J, Pan M-H, Cheng A-L, Lin L-I, Ho Y-S, Hsieh C-Y, Lin J-K. J Pharmaceut
Biomed Anal 1997;15:1867-1876.
16
Table 1
Chemical composition of the antioxidants studied
Commercial name
Chemical composition
Molecular mass (g/mol)
Curcumin O O
OH OH
OO
CH3 CH3
O OH
OH OH
OO
CH3 CH3
368
Irganox 1010
1178
P P
O
O O
O
1035
P
O
O
595
Sandostab P-EPQ
Diphosphonite >70%
Monophosphonite ~20%
Phosphite <10%
HO
O
O
C
4
P
O
OO
647
17
Figure captions
Fig. 1 Thermograms (melting) of curcumin, P-EPQ, and a 1:1 mixture of curcumin and P-
EPQ measured under nitrogen after melting in Ar atmosphere at 220 °C for 1 min
and then cooling down to ambient temperature. Heating rate: 10 °C/min.
Fig. 2 UV-VIS spectra of curcumin recorded before aging (), and after aging at ambient
temperature for 147 days in powder form in dark (− − −) and light (−· ̶ ·), as well as
in methanol solution in dark (····).
Fig. 3 UV-VIS spectra of curcumin measured before aging (), and after aging in
methanol solution in light at ambient temperature for various times: − − − 17, −· ̶ ·
28, −·· ̶ ·· 56, and ···· 147 days.
Fig. 4 The stabilization effect of H-bonds on the light stability of curcumin in solution.
Solvents: () ethanol, () methanol, () acetone, () acetonitrile, () toluol,
() chloroform
Fig . 5 Effect of the number of extrusions on the vinyl group content of polyethylene
stabilised with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000 ppm P-EPQ
(●), 1000 ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■).
Fig. 6 Effect of the number of extrusions on the carbonyl group content of polyethylene
stabilised with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000 ppm P-EPQ
(●), 1000 ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■).
Fig. 7 Effect of the number of extrusions on the melt flow rate of polyethylene stabilised
with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000 ppm P-EPQ (●), 1000
ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■) Neat powder (▲).
Fig. 8 Effect of the number of extrusions on the creep viscosity of polyethylene stabilised
with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000 ppm P-EPQ (●), 1000
ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■).
18
Fig. 9 Effect of the number of extrusions on the residual thermo-oxidative stability of
polyethylene stabilised with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000
ppm P-EPQ (●), 1000 ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■).
Fig. 10 Effect of the number of extrusions on the yellowness index of polyethylene
stabilised with 1000 ppm curcumin (○), 1000 ppm curcumin + 2000 ppm P-EPQ
(●), 1000 ppm I1010 (□), and 1000 ppm I1010 + 2000 ppm P-EPQ (■).
19
Fig. 1
20
Fig. 2
21
Fig. 3
22
Fig. 4
23
Fig. 5
24
Fig. 6
25
Fig. 7
26
Fig. 8
27
Fig. 9
28
Fig. 10
29